The utility model provides a free compound detection electrode structure of super capacitor and detection device. The complex detection electrode structure includes electric capacity detection electrode and resistance detection probe, the resistance detection probe embedded in among the said electric capacity detection electrode, and can follow stretch out among the electric capacity detection electrode, electric capacity detection electrode with between the resistance detection probe is provided with the insulating layer. The utility model provides a free compound detection electrode structure of super capacitor and detection device detects the free appearance value of super capacitor by electric capacity detection electrode, detects the free resistance of super capacitor by the resistance detection probe, and provide the insulating layer between electric capacity detection electrode and resistance detection probe, detects when having realized free resistance of super capacitor and appearance value, has improved the free detection efficiency to super capacitor, has just reduced detection electrode's resistance itself and to the interference of the free resistance of super capacitor, has improved the detecting accuracy to the free resistance of super capacitor.